CN109153926A

CN109153926A - Conversion of the crude oil to petrochemical

Info

Publication number: CN109153926A
Application number: CN201780029295.7A
Authority: CN
Inventors: 丁连辉; 埃萨姆·阿尔-萨伊德; 杜海曼·U·阿尔-雅美; 阿布德努尔·布兰; 阿尔贝托·洛扎诺·巴列斯特罗斯; 易卜拉欣·阿巴
Original assignee: Saudi Arabian Oil Co
Current assignee: Saudi Arabian Oil Co
Priority date: 2016-05-13
Filing date: 2017-05-09
Publication date: 2019-01-04
Anticipated expiration: 2037-05-09
Also published as: JP6895994B2; JP2019520443A; KR20190008287A; CN109153926B; KR102335299B1; US10563141B2; SG11201810050SA; WO2017196791A1; SA518400414B1; US20170327754A1; EP3455335A1; EP3455335B1

Abstract

The embodiment of the integrated hydrotreating and steam pyrolysis process of processing crude oil includes the higher fraction of the crude oil of recycling upgrading to improve the yield of the petrochemical such as alkene and aromatic hydrocarbons.

Description

Conversion of the crude oil to petrochemical

Technical field

This disclosure relates to a kind of integrated hydrotreating for processing crude oil and steam pyrolysis process, wherein recycling upgrading The heavy distillat of crude oil is to improve the yield of the petrochemical such as alkene and aromatic hydrocarbons.

Background technique

Light alkene (such as ethylene, propylene, butylene, butadiene and C₄Derivative) and aromatic hydrocarbons (such as benzene, toluene and diformazan Benzene) it is widely used in the basic and required intermediary of petrochemistry and chemical industry.Thermal cracking or steam pyrolysis are to be formed The main method type of these materials, usually in the presence of steam and in the presence of no oxygen.Raw material for pyrolysis can wrap Containing petroleum gas and distillate, such as naphtha, kerosene and gas oil.However, these raw materials availability usually it is limited and At high cost and energy-intensive method and step is needed in crude oil refineries.

Heavy hydrocarbon has been used to be studied as the raw material of steam pyrolysis reactor.Conventional heavy hydrocarbon steam pyrolysis operation Major defect be coke formation.

In addition, heavy hydrocarbon is used to be different from as the yield and distribution of the alkene of the raw material of steam pyrolysis reactor and aromatic hydrocarbons Use those of hydrocarbon feedstock.Heavy hydrocarbon has arene content and higher boiling point bigger compared with light hydrocarbon.It is biggish Armaticity can be indicated by biggish mineral bureau's index of correlation (BMCI).BMCI is the measured value of the armaticity of raw material and calculating It is as follows:

BMCI=87552/VAPB+473.5* (sp.gr.) -456.8 (1)

Wherein:

Volume average boiling point of the VAPB=as unit of Rankine degree, and

The specific gravity of sp.gr.=raw material.

As BMCI is reduced, it is contemplated that ethylene yield will improve.Therefore, height alkane or low aromatic feed are commonly used in steaming Vapour is pyrolyzed to obtain the required alkene of higher yields and avoid the non-required production for having higher yields in reactor coil section Object and coke formation.In view of this boiling point difference, this specification can also utilize higher fraction simultaneously when referring to heavy hydrocarbon And when referring to light hydrocarbon using compared with low-boiling fraction.

In order to the demand growing in response to these petrochemicals, the other types of original that can largely obtain Expect that (such as crude oil) is attractive to the producer." crude oil " is interpreted as comprising the whole crude from usual sources, and Undergo some pretreated crude oil.Term " crude oil " is also understood as comprising having been subjected to water-oil separation, gas-oil separation, taking off The crude oil of salt, stabilisation or combinations thereof.It is raw as these petrochemicals that refinery will be minimized or eliminated using crude oil feeding A possibility that producing bottleneck.Current integrated crude oil adjusts process for steam cracking can not be efficiently by the heavy distillat of the crude oil of upgrading It is converted into the petrochemical such as alkene and aromatic hydrocarbons, and leads to high-caliber coke formation.

Summary of the invention

Accordingly, it has been required to which improved converting crude oil method, realizes the yield of the petrochemical such as alkene and aromatic hydrocarbons It improves and the horizontal of coke formation reduces.

Embodiment of the disclosure is by providing integrated hydrotreating and steam pyrolysis process for directly processing crude oil Meet those needs, wherein recycling the heavy distillat of the crude oil of upgrading to improve the production of the petrochemical such as alkene and aromatic hydrocarbons Rate.

According to one embodiment, a kind of method for upgrading crude oil is provided.The method includes mixing crude stream and hydrogen stream It closes to obtain crude oil and hydrogen mixture；With by the crude oil and hydrogen be transmitted to 300 to 450 degrees Celsius (C) temperature and The hydrotreating reactor operated under 30 to 200 bars of pressure.The hydrotreating reactor includes hydrotreating catalyst.Institute State hydrotreating catalyst may be used to the crude oil and hydrogen mixture hydrodesulfurization, hydrodemetallization, hydrodenitrogeneration (or A combination thereof) to generate the mixture of hydrotreating.The method further includes being transmitted to the mixture of the hydrotreating Separator unit is being separated into the mixture of the hydrotreating compared with low-boiling fraction and higher fraction.It is described more high boiling Point fraction has density of aromatic hydrocarbon and higher boiling point bigger compared with the lower fraction, and the higher fraction has At least 500 DEG C of boiling point.The method further includes being that the steam operated under 700 to 900 DEG C of coil outlet temperature is split Change in furnace described in thermal cracking compared with low-boiling fraction include to obtain alkene and aromatic hydrocarbons cracking effluent, and described in recycling it is higher Boiling point fraction is to mix in the hydrotreating reactor upstream with the crude oil with hydrogen mixture to promote the crude oil Further upgrading.

The additional features and advantage of embodiment will illustrate in specific embodiment below, and will be partly to ability The technical staff in domain be easily aware of or by practice embodiments described herein (including following description, Claims and attached drawing) and recognize.

Detailed description of the invention

Fig. 1 is the process flow chart of an embodiment of integrated hydrotreating and steam pyrolysis process, wherein recycling rises The higher fraction of the crude oil of grade.

Fig. 2 is the process flow chart of another embodiment of integrated hydrotreating and steam pyrolysis process, wherein recycling The higher fraction of the crude oil of upgrading.

Fig. 3 is the process flow chart of another embodiment of integrated hydrotreating and steam pyrolysis process, wherein recycling The higher fraction of the crude oil of upgrading.

Fig. 4 is the process flow chart of another embodiment of integrated hydrotreating and steam pyrolysis process, wherein recycling The higher fraction of the crude oil of upgrading.

Embodiment described in schema is substantially illustrative, it is therefore intended that limitation claims.In addition, in view of tool The Individual features of body embodiment, schema will be more completely aware and understood.

Specific embodiment

Embodiment of the disclosure is integrated hydrotreating and the steam pyrolysis process being directed to for directly processing crude oil, The higher fraction of the crude oil of middle recycling upgrading is to improve the yield of the petrochemical such as alkene and aromatic hydrocarbons.

Process flow chart is showed in Fig. 1 to 4, and it includes integrated hydrotreating and steam pyrolysis process, wherein following again The higher fraction of the crude oil of ring upgrading.In some embodiments, the method for upgrading crude oil includes by crude stream 101 and hydrogen 102 mixing of stream is to obtain crude oil and hydrogen mixture 112.As described previously, " crude oil " is interpreted as comprising from conventional next The whole crude in source, and have been subjected to some pretreated crude oil.In some embodiments, " crude oil " may include from very The crude oil for advising source, such as pressure break light oil and other natural gas condensates.Term " crude oil " is also understood as comprising having been subjected to The crude oil of water-oil separation, gas-oil separation, desalination, stabilisation or combinations thereof.In some embodiments of method, crude stream 101 With 25 ° to 50 ° of API severe (°).For example and as described in Fig. 2 to 4, crude stream 101 can with hydrogen stream Pump 103 is passed through before 102 mixing optionally first to generate the crude stream 104 of pressurization.Therefore, in certain embodiments, The method includes pressurized crude oil stream 101.In some embodiments, crude stream 101 or the crude stream 104 of pressurization can transmit logical The crude oil steam 106 that heater 105 is crossed to generate preheating crude stream or preheating respectively and pressurize.Therefore, certain In embodiment, the method includes the temperature that crude stream 101 is pre-heated to at least 300 DEG C before mixing with hydrogen stream 102. In some embodiments, hydrogen stream 102 can be the hydrogen of introduction, by hydrogen of downstream units recycling or combinations thereof.It can be with The hydrogen 119 of recycling is provided for the downstream units of hydrogen steam 120 including, for example, optional high pressure is cold or heat separator 116, steam cracker furnace 140 and a combination thereof.In certain embodiments, the method comprising using the upgrading crude oil of the hydrogen of recycling The hydrogen of bottom line purging recycling be may further include to avoid the contamination build-up in recirculation circuit.In addition, Hydrogen stream can with the crude stream 104 of crude stream 101, pressurization or preheat and before the crude oil steam 106 that pressurizes mixes Pass through compressor 107 optionally to generate the hydrogen stream 108 of pressurization.In addition, hydrogen stream can with crude stream 101, plus The crude stream 104 of pressure or the Optional for 106 mixing of crude oil steam for preheating and pressurizeing pass through heater 109 to produce Raw preheating hydrogen stream or preheating and the hydrogen stream 111 pressurizeed.In some embodiments, heater is to by hydrogen stream (or hydrogen stream of pressurization) is heated at least 300 DEG C of temperature.

In some embodiments, the method for upgrading crude oil further comprises being transmitted to crude oil and hydrogen mixture 112 to add Hydrogen treatment reactor 120.Hydrotreating reactor 120 includes for receiving the entrance of crude oil and hydrogen mixture 112 and being used for Discharge the outlet of the mixture 122 of hydrotreating.In certain embodiments, hydrotreating reactor 120 effectively make crude oil with Under 112 hydrodemetallization of hydrogen mixture, hydrogenation aromatics-removing, hydrodenitrogeneration, hydrodesulfurization, the parameter that is hydrocracked or combinations thereof Operation, therefore generate the mixture 122 of hydrotreating.For example, in some embodiments, hydrotreating reactor 120 can With 300 to 450 DEG C at a temperature of operate.Other temperature ranges include 300 to 330 DEG C, 300 to 350 DEG C, 320 to 360 DEG C, 340 to 380 DEG C, 360 to 400 DEG C, 380 to 420 DEG C, 400 to 430 DEG C and 420 to 450 DEG C.In some embodiments, add at hydrogen Reason reactor 120 can operate under 30 to 200 bars of pressure.Other pressure limits include 30 to 60 bars, 30 to 100 bars, 50 To 100 bars, 75 to 125 bars, 100 to 150 bars, 125 to 175 bars and 150 to 200 bars.In some embodiments, hydrotreating is anti- The liquid hourly space velocity (LHSV) (LHSV) for answering device 120 is 0.1 to 2.0h^-1.Other LHSV ranges include 0.1 to 0.5h^-1, 0.5 arrive 1.0h^-1、 1.0 arrive 1.5h^-12.0h is arrived with 1.5^-1。

In certain embodiments, as known in the art, hydrotreating reactor 120 may include one or more A unit operation.For example, hydrotreating reactor 120 may include multiple reaction vessels, respectively contain a effective amount of One or more catalyst, such as Hydrodemetalation catalyst, and there is hydrogenation aromatics-removing, hydrodenitrogeneration, hydrodesulfurization plus hydrogen to split Change the hydrotreating catalyst of function or combinations thereof.Alternatively, hydrotreating reactor 120 may include one or more points From area, respectively contain a effective amount of Hydrodemetalation catalyst and it is a effective amount of have hydrogenation aromatics-removing, hydrodenitrogeneration, plus Hydrogen desulfurization, the hydrotreating catalyst for being hydrocracked function or combinations thereof.Alternatively, hydrotreating reactor 120 can wrap Containing one or more catalyst layers, contain a effective amount of Hydrodemetalation catalyst；With one or more catalyst layers, contain Having a effective amount of has the function of hydrogenation aromatics-removing, hydrodenitrogeneration, hydrodesulfurization, the hydrorefining catalyst being hydrocracked or combinations thereof Agent.In some embodiments, as known in the art, hydrotreating reactor 120 may include one or more hydrogen Gas quenching.One or more hydrogen are quenched for controlling the reaction temperature in hydrotreating reactor, and by adding at hydrogen It manages and is introduced between one or more reaction vessels, one or more Disengagement zone or the one or more catalyst layers of reactor 120 Hydrogen stream is realized.For hydrogen quenching hydrogen stream can be introduction hydrogen, by downstream units recycling hydrogen or its Combination.The hydrogen of recycling can be provided for the downstream units of hydrogen quenching including, for example, optional high pressure is cold or heat separator Or steam, steam cracker furnace 140 and a combination thereof.

In some embodiments, hydrotreating reactor 120 includes multiple catalyst layers.As described in Fig. 2 to 4, add Hydrogen treatment reactor 120 may include two or more catalyst layers 123 and 124.In other embodiments, hydrotreating is anti- Answering device 120 includes multiple reaction vessels, respectively contains one or more catalyst layers, such as the catalyst with different function Layer.In certain embodiments, hydrotreating reactor 120, which may include, makes crude oil with hydrogen mixture demetalization and desulfurization to produce The hydrotreating catalyst of the mixture 122 of raw hydrotreating.In some embodiments, hydrotreating catalyst includes at least one Kind of the metal from the 8 to 10th race of the periodic table of elements, metal at least from the 6th race or at least one from the 8 to 10th race The combination of metal and at least one metal from the 6th race.In other embodiments, hydrotreating catalyst include cobalt (Co) and Nickel (Ni).In other embodiments, hydrotreating catalyst includes the molybdenum (Mo) and tungsten (W) being carried on carrier material.At certain In a little embodiments, carrier material includes aluminium oxide.

In some embodiments, hydrotreating reactor 120 includes Hydrodemetalation catalyst.In other embodiments, Hydrodemetalation catalyst may be embodied in independent reaction vessel (not shown) or Disengagement zone.For example, in certain implementations In example, Hydrodemetalation catalyst is included in the catalyst layer separated with other catalyst layers.In other embodiments, add hydrogen Catalyst for demetalation may be embodied in independent reaction vessel (not shown) or be separately separated in area.In certain embodiments, add hydrogen Catalyst for demetalation can be carried on carrier material.In some embodiments, carrier material includes aluminium oxide.In certain implementations In example, Hydrodemetalation catalyst can be based on gamma-alumina carrier material, and surface area is 140 to 240 meters²/ gram (m²/g).Its Its surface area includes 140 to 160m²180m is arrived in/g, 160²200m is arrived in/g, 180²220m is arrived in/g, 200²/ g and 220 is arrived 240m²/g.This catalyst has high pore volume, such as more than 1 centimetre³/ gram (cm³/g).Pore size itself is usually main If macropore, it is greater than 75 microns (μm) of hole.This is to provide on catalyst surface and optionally dopant golden Belong to the large capacity absorbed.Active metal on catalyst surface is that the ratio of Ni and Mo is the sulfide of Ni/Ni+Mo < 0.15.Add Ni concentration on hydrogen catalyst for demetalation is lower than other catalyst because expected some Ni and vanadium (V) during removal itself by Deposits materials serve as catalyst.The dopant used can be one of phosphorus (P), boron (B), silicon (Si) and halogen or a variety of. In certain embodiments, catalyst can be the form of alumina extrudate or alumina beads.In other embodiments, it aoxidizes Aluminium pill grain is for promoting the unloading of catalyst hydrogenation demetallised layer in the reactor, because range of the Metal absorption at the top of layer exists Between 30 to 100%.

In certain embodiments, hydrotreating reactor 120 includes Intermediate Catalyst.Intermediate Catalyst can be also used for into Transformation between row hydrodemetallization and hydrodesulfurization function.In some embodiments, Intermediate Catalyst may be embodied in individually In reaction vessel (not shown) or Disengagement zone.In some embodiments, Intermediate Catalyst is included in Hydrodemetalation catalyst. For example, Intermediate Catalyst may be embodied in hydrogenation metal catalyst layer.In some embodiments, Intermediate Catalyst packet It is contained in Hydrobon catalyst.For example, Intermediate Catalyst may be embodied in Hydrobon catalyst layer.In certain realities It applies in example, Intermediate Catalyst is included in independent catalyst layer.For example, Hydrodemetalation catalyst, Intermediate Catalyst and Hydrobon catalyst is included in independent catalyst layer.In some embodiments, Intermediate Catalyst can be carried on carrier material On material.Carrier material may include aluminium oxide.Intermediate Catalyst may include intermetallic metal load capacity and pore size distribution.It urges Agent may include the alumina-based supports of extrudate form, it is optionally at least a kind of from the 6th race catalytic metal (such as Mo, W or combinations thereof) or at least one catalytic metal (such as Ni, Co or combinations thereof) or combinations thereof from the 8 to 10th race.In Between catalyst can also optionally contain at least one dopant selected from B, P, Si and halogen.Physical property is arrived comprising 140 200m²The surface area of/g.Other surface areas include 140 to 160m²180m is arrived in/g, 160²/ g or 180 arrives 200m²/g.Physics Property also includes at least 0.6cm³The pore volume of/g.Physical property further includes for mesoporous and at 12 to 50 nanometers (nm) Hole in range.Other ranges include 12 to 20nm, 20 to 30nm, 30 to 40nm or 40 to 50nm.

In some embodiments, hydrotreating reactor 120 includes Hydrobon catalyst.In some embodiments, add Hydrogen desulphurization catalyst may be embodied in independent reaction vessel (not shown) or Disengagement zone.For example, Hydrobon catalyst It may be embodied in the catalyst layer separated with other catalyst layers.In certain embodiments, Hydrodemetalation catalyst, centre Catalyst and Hydrobon catalyst are included in independent catalyst layer.In certain embodiments, Hydrodemetalation catalyst can To be carried on carrier material.In some embodiments, carrier material includes aluminium oxide.In some embodiments, hydrodesulfurization Catalyst may include with those of alumina-based supports material, surface area towards the upper end of hydrodemetallization range, such as Range is 180 to 240m²/g.Other ranges include 180 to 195m²210m is arrived in/g, 195²225m is arrived in/g, 210²/ g or 225 is arrived 240m²/g.This needs biggish hydrodesulfurization surface, leads to relatively small pore volume, is, for example, less than 1cm³/g.Add hydrogen de- Sulfur catalyst contains at least one element from the 6th race, such as Mo；With at least one element from the 8 to 10th race, such as Ni. Catalyst further includes at least one dopant selected from B, P, Si and halogen.In certain embodiments, cobalt is for providing opposite increasing The desulfurization level added.With required active increase, the content of metal of active phase increases, so that the molar ratio of Ni/Ni+Mo exists In 0.1 to 0.3 range, and (Co+Ni)/Mo molar ratio is in 0.25 to 0.85 range.

In certain embodiments, hydrotreating reactor 120 may include be designed to carry out raw material hydrogenation (rather than add The major function of hydrogen desulfurization) final catalyst, such as such as " applied catalysis A: general rule (Appl.Catal.A General) ", Described in 204 (2000) 251.In other embodiments, final catalyst may be embodied in independent reaction vessel (not shown) or In Disengagement zone.For example, final catalyst may be embodied in the catalyst layer separated with other catalyst layers.In certain realities It applies in example, final catalyst can be carried on carrier material.In certain embodiments, carrier material may include aluminium oxide. Final catalyst can be promoted by Ni.Physical property includes the surface area towards the relatively big end of range, such as 180 arrive 240m²/g.Its Its range includes 180 to 195m²210m is arrived in/g, 195²225m is arrived in/g, 210²/ g and 225 arrives 240m²/g.This needs increased table Face is hydrogenated, and relatively small pore volume is caused, and is, for example, less than 1cm³/g。

Referring to figs. 1 to 4, the method for upgrading crude oil optionally further comprises that cooling comes from heat exchanger (not shown) The mixture 122 of the hydrotreating of hydrotreating reactor 120, and by the mixture 122 of hydrotreating be transmitted to high pressure it is cold or Heat separator 116.The gas and product liquid for the mixture 122 that high pressure is cold or heat separator 116 is for separating hydrotreating.? Clean separation device tops 117 in amine unit 118, and the gas stream 113 of gained hydrogen rich gas is optionally delivered to recycling pressure Contracting machine 114 for use as the recycling in hydrotreating reactor 120 gas 119.Basic upper liquid from high-pressure separator 116 The bottoms 115 of phase are cooled and are introduced into low pressure cold separator 121, it is separated into gas in the low pressure cold separator Body stream and liquid flow 125.Gas from low pressure cold separator 121 includes hydrogen, H₂S、NH₃With any light hydrocarbon, such as C1-C4 Hydrocarbon.These gases can such as dodge flame processing or fuel gas disposal optionally by being further processed.

Referring to figs. 1 to 4, the method for upgrading crude oil further comprises transmitting the liquid flow 125 from low pressure separator 121 To separator unit 130.Separator unit 130 be used for by hydrotreating mixture 122 higher fraction 132 separation compared with Low-boiling fraction 131.In some embodiments, higher fraction 132 has at least 500 DEG C of boiling point.In some embodiments In, there is the boiling point lower than 500 DEG C compared with low-boiling fraction 131.In other embodiments, have compared with low-boiling fraction 131 and be lower than 500 DEG C of boiling spreads arrived lower than 560 DEG C, and higher fraction 132 has higher than 500 DEG C to the boiling point models for being higher than 560 DEG C It encloses.Feature and composition compared with low-boiling fraction 131 include light naphtha fraction, heavy naphtha fraction, kerosene distillate, diesel oil distillate And gas oil fraction of the boiling point between 370 DEG C and 540 DEG C.The feature and composition of higher fraction 132 are higher than comprising boiling point 540 DEG C of vacuum residue fraction.It therefore, include " < C bigger compared with higher fraction 132 compared with low-boiling fraction 131₄₀ Hydrocarbon " (hydrocarbon having less than 40 carbon atoms) concentration, and higher fraction 132 has compared with compared with low-boiling fraction 131 more Big " > C40 " hydrocarbon (there is the hydrocarbon more than 40 carbon atoms) concentration.In addition, higher fraction 132 includes to evaporate with compared with low boiling point 131 are divided to compare bigger density of aromatic hydrocarbon.Separator unit 130 includes for receiving the entrance of the mixture 122 of hydrotreating, using In outlet of the discharge compared with the outlet of low-boiling fraction 131 and for discharging higher fraction 132.

It is expected that various assemblies are used for separative unit 130.In certain embodiments, described as in Figures 3 and 4, separative unit 130 include flash chamber 133 and the distillation container 136 in 133 downstream of flash chamber.In some embodiments, separative unit 130 It may include one or more flash chambers 133.In certain embodiments, flash chamber 133 is flash tank.In upgrading crude oil It include by the mixture of the hydrotreating in flash chamber 133 by the separation of separator unit 130 in some embodiments of method 122 are separated into first compared with low-boiling fraction 134 and the first higher fraction 135, wherein first has compared with low-boiling fraction 134 Boiling spread lower than 350 DEG C, and the first higher fraction 135 has the boiling spread higher than 350 DEG C.First compared with low boiling The feature and composition of point fraction 134 include light naphtha fraction, heavy naphtha fraction, kerosene distillate and diesel oil distillate.First compared with The feature and composition of high boiling fraction 135 include that gas oil fraction and boiling point of the boiling point between 370 DEG C and 540 DEG C are higher than 540 DEG C vacuum residue fraction.Therefore, first compared with low-boiling fraction 134 include compared with the first higher fraction 135 it is bigger “<C₁₈" hydrocarbon (hydrocarbon having less than 18 carbon atoms) concentration, and the first higher fraction 135 have evaporated with first compared with low boiling point 134 are divided to compare bigger " > C₁₈" hydrocarbon (there is the hydrocarbon more than 18 carbon atoms) concentration.Flash chamber 133 may include for connecing Receive the entrance of the mixture 122 of hydrotreating and for discharging first compared with the outlet of low-boiling fraction 134 and for discharging first The outlet of higher fraction 135.In certain embodiments, the mixture 122 of hydrotreating is in flash chamber 133 in atmosphere It is flashed under pressure and the inlet temperature between 350 DEG C and 450 DEG C.Other inlet temperatures include 350 to 370 DEG C, 370 to 390 DEG C, 390 to 410 DEG C, 410 to 430 DEG C and 430 to 450 DEG C.

With reference to Fig. 3 and 4, in certain embodiments, the method for upgrading crude oil further comprises by the first higher fraction 135 are transmitted to distillation container 136.In some embodiments, separative unit 130 may include one or more distillation containers 136. In certain embodiments, distillation container 136 can be destilling tower, such as vacuum (distilling) column.Therefore, upgrade some of the method for crude oil Embodiment further comprises the first higher fraction 135 in separation distillation container 136 to obtain second compared with low-boiling fraction 137 and higher fraction 132, wherein second has compared with low-boiling fraction 137 and is higher than 350 DEG C to the boiling point models lower than 500 DEG C It encloses, and higher fraction 132 has the boiling point higher than 500 DEG C.In other embodiments, second compared with low-boiling fraction 137 It arrives with being higher than 350 DEG C lower than 500 DEG C to the boiling spreads lower than 560 DEG C, and higher fraction 132 has higher than 500 DEG C to higher than 560 DEG C of boiling spread.Second compared with low-boiling fraction 137 feature and composition comprising boiling point in 370 DEG C and 540 DEG C Between gas oil fraction.As described previously, the feature of higher fraction 132 and composition include boiling point higher than 540 DEG C Vacuum residue fraction.Therefore, second includes C bigger compared with higher fraction 132 compared with low-boiling fraction 137₁₈-C₄₀Hydrocarbon Concentration, and higher fraction 132 has " > C bigger compared with second compared with low-boiling fraction 137₄₀" hydrocarbon concentration.Distill container 136 may include entrance for receiving the first higher fraction 135, for discharging the second going out compared with low-boiling fraction 137 Mouth and the outlet for discharging higher fraction 132.In certain embodiments, temperature of the destilling tower between 350 DEG C and 450 DEG C It is operated under degree and 10 millimeters of mercury (mmHg) to the absolute pressure between 40mmHg.Other absolute pressure ranges are arrived comprising 10 40mmHg is arrived in 20mmHg, 20 to 30mmHg and 30.

Referring to figs. 1 to 4, in some embodiments, the method for upgrading crude oil further comprises that will come from separator unit 130 Relatively low-boiling fraction 131 be transmitted to steam cracker furnace 140.In separative unit 130 including flash chamber 133 and in flash chamber In the embodiment of the distillation container 136 in 133 downstreams, the method for upgrading crude oil may further include to be combined in mixer 138 From flash chamber 133 first compared with low-boiling fraction 134 with from distillation container 136 second compared with low-boiling fraction 137 with It obtains compared with low-boiling fraction 131.Therefore, in some aspects, the method further includes in steam cracker furnace 140 in steam Thermal cracking is compared with low-boiling fraction 131 in the presence of 142.Steam cracker furnace 140 will be effectively required compared with 131 cracking of low-boiling fraction It is operated under the parameter of product, the required product (includes comprising alkene (including ethylene, propylene, butylene and butadiene), aromatic hydrocarbons Benzene, toluene and dimethylbenzene), pyrolysis gasoline, pyrolysis gas oil and pyrolysis oil.In certain embodiments, steam cracker furnace 140 exists At a temperature of 700 to 900 DEG C operate with obtain include alkene and aromatic hydrocarbons cracking effluent 141.Other possible temperature ranges Include 700 to 750 DEG C, 750 to 800 DEG C, 800 to 850 DEG C or 850 to 900 DEG C.

With reference to Fig. 4, in some embodiments, steam cracker furnace 140 is including convection current section 143 and under convection current section 143 The pyrolysis section 145 of trip.Convection current section 143 and pyrolysis section 145 can be based on the behaviour of steam pyrolysis unit known to technical staff Make and operate, that is to say, that convection current section 143 will be transmitted in the presence of steam 142 compared with low-boiling fraction 131.Serve as pyrolysis The relatively low-boiling fraction 131 of feeding flow is transmitted to convection current section in the presence of a effective amount of steam, such as through steam inlet first 143 entrance." a effective amount of steam " acts as diluent with the steam for keeping the hydrocarbon molecule compared with low-boiling fraction 131 to separate Amount.It arranges, will be evaporated compared with low boiling point in convection current section 143, such as using one or more waste heat flux or other suitable heating 131 are divided to be heated to predetermined temperature with 142 mixture of steam.In certain embodiments, temperature of the convection current section 143 at 700 to 900 DEG C The lower operation of degree.Other temperature ranges may include 700 to 750 DEG C, 750 to 800 DEG C, 800 to 850 DEG C or 850 to 900 DEG C.Come From light fraction 144 after relatively low-boiling fraction 131 and 142 mixture of extra steam the formation convection current of the heating of general segments 143.

Still referring to FIG. 4, in some embodiments, light section 144 is transmitted to pyrolysis section from general segments 143 after convection current 145.Pyrolysis section 145 operates under the parameter of light 144 cracking cracking effluent 141 of section after effectively making convection current.Cracked stream Object 141 includes required product out, (includes benzene, toluene and two comprising alkene (including ethylene, propylene, butylene and butadiene), aromatic hydrocarbons Toluene) and pyrolysis gasoline.In certain embodiments, the steam cracking in convection current section 143 and pyrolysis section 145 uses convective region In section 143 and pyrolysis section 145 within the scope of 700 DEG C to 900 DEG C temperature, in convection current section 143 in 0.3:1 to 2.0:1 model In 0.05 second to 2 seconds range in steam 142 and 132 ratio of light fraction and convection current section 143 and pyrolysis section 145 in enclosing The interior residence time carries out.

Referring to figs. 1 to 4, in some embodiments, the method for upgrading crude oil further comprises being recycled for from separator list The higher fraction 132 of member 130 is so as in 120 upstream of hydrotreating reactor and (or alternatively, the pressurization of crude stream 101 Crude stream 104 or preheat and the crude oil steam 106 that pressurizes) and (or alternatively, the hydrogen stream of pressurization of hydrogen stream 102 108) the further upgrading to promote crude oil is mixed.In certain embodiments, higher fraction 132 is recycled to mixer 110 so as to crude stream 101 (or alternatively, the crude stream 104 of pressurization or preheat and the crude oil steam 106 that pressurizes) and Hydrogen stream 102 (or alternatively, the hydrogen stream 108 of pressurization) mixing.Unexpectedly, it is recycled for from separator unit 130 The higher fraction 132 of the unconverted oil of (and alternatively from distillation container 136) is led further to upgrade crude oil Causing alkene (including ethylene, propylene, butylene and butadiene) and aromatic hydrocarbons in steam cracker furnace 140 (includes benzene, toluene and diformazan Benzene) yield relative to do not include higher fraction 132 such recycling method improve.In certain embodiments, it wraps The method of the upgrading crude oil of the higher fraction 132 containing recycling leads at least one of ethylene, propylene, butylene and butadiene Yield improve.In other embodiments, the method comprising recycling the upgrading crude oil of higher fraction 132 leads to benzene, first The yield of at least one of benzene and dimethylbenzene improves.In addition, such be recycled for from separator unit 130 (and alternatively From distillation container 136) the higher fraction 132 of unconverted oil lead to steam cracker furnace further to upgrade crude oil Coke formation in 140 is reduced relative to the method for the such recycling for not including higher fraction 132.In some embodiments In, it is more high boiling that the method for the upgrading crude oil comprising recycling higher fraction 132 may further include bottom line purging Fraction 132 is put to avoid the contamination build-up in recirculation circuit.

In some embodiments, the method for upgrading crude oil further comprises cooling cracking effluent 141.In some embodiments In, the method includes cracking effluent 141 to be cool below to 200 DEG C of temperature, such as environment temperature to 200 DEG C it Between.In some embodiments, as known in the art, the method for upgrading crude oil further comprises that cracking effluent is delivered to volume Outer separative unit 150, such as cooler, gas-liquid separator, air oil actuator, oil-liquid/gas separator, fractionator or combinations thereof.Separately Outside, in some embodiments, as known in the art, the method for upgrading crude oil further comprises in fractionator 150 by cracking Effluent 141 separates alkene.

For example, cracking effluent 141 can for delivery to quenching area's (not shown) entrance, quenching solution (such as water, Pyrolysis fuel oil or combinations thereof) it is rapid with the centre for generating the reduction temperature with such as 200 DEG C to 300 DEG C through the introducing of independent entrance Cold mix products stream, and discharge useless quenching solution.Admixture of gas effluent from steam cracker furnace 140 is usually hydrogen Gas, methane, hydrocarbon, carbon dioxide and hydrogen sulfide mixture.It, can be in compound compressor area after cooling with water or oil quenching In, for example, in 4 to 6 grades compressed mixture to generate the admixture of gas of compression.It can be in caustic alkali processing unit for processing The admixture of gas of compression exhausts the admixture of gas of hydrogen sulfide and carbon dioxide to generate.It can be further in compressor area Compressed gas mixtures, and the gas of gained cracking is usually subjected to low-temperature treatment to be dehydrated, and by using molecular sieve into One step is dry.

In addition, the gas stream of cold cracking can be generated by it for delivery to domethanizing column (not shown) and carry out cracking gas The tower top stream containing hydrogen and methane of body stream.Then bottoms from domethanizing column can be transported in product Disengagement zone In be further processed, the product Disengagement zone includes fractionating column, include dethanizer, depropanizing tower and debutanizing tower.It can be with Using the Process configuration of domethanizing column, dethanizer, depropanizing tower and debutanizing tower with different order.

It is domethanizing column and methane separation and in hydrogen recovery unit after hydrogen recycling, obtaining has usual 80 To the hydrogen of the purity of 95 volume % (vol%).Recovery method in hydrogen recovery unit include low temperature recycling (such as about- At a temperature of 157 DEG C).Hydrogen stream then can be for delivery to hydrogen purification unit, such as pressure-variable adsorption (PSA) unit, to be had There is the hydrogen stream of 99.9%+ purity；Or film separation unit, to obtain the hydrogen stream with about 95% purity.The hydrogen stream of purifying Then it can be recycled back to serve as most of required hydrogen of hydrotreating zone.In addition, small percentage can be used for acetylene, The hydrogenation of allylene and allene.In addition, the methane stream from hydrogen recovery unit can be optionally recycled to steam Vapour cracker for use as burner, heater or combinations thereof fuel.

In addition, the bottoms from domethanizing column can be transported to the entrance of product Disengagement zone to be separated into methane, second Alkene, propylene, butadiene, mixed butene and pyrolysis gasoline can be discharged through independent outlet.Pyrolysis gasoline generally comprises C₅-C₉ Hydrocarbon, and benzene, toluene and dimethylbenzene can be extracted from this fraction.

The feature of the embodiment of the present invention will be further illustrated in the following example.

Example

The higher fraction for recycling the crude oil of upgrading causes the yield of aromatic hydrocarbons and alkene to improve:

As shown in table 1, according to previously described method, research is compared to assess the original of steam cracking hydrotreating Petrochemical yield of the oil in the case where recycling higher fraction and not recycling higher fraction.SPYRO is soft Part (the Technip Benelux B.V. for being located at Zultmel ,Holland (Zoetermeer, Netherlands)) is steamed for simulating Vapour cracking process.The machined parameters of SPYRO simulation include 700 DEG C to 900 DEG C of temperature, the steam and hydrocarbon ratio of 0.3:1 to 2.0:1 Rate and 0.05 second to 0.2 second residence time.Table 1 lists the extra condition of steam cracker.

If described in table 1, recycle the crude oil of upgrading higher fraction cause the yield of aromatic hydrocarbons and alkene with not The same procedure of such recycling comprising higher fraction is compared to improve.

Table 1

It should not be understood, the various aspects for describing composite zeolite catalyst, the method for manufacturing catalyst are manufactured using catalyst The method of dimethylbenzene and the system for manufacturing dimethylbenzene using catalyst, and such aspect can make in conjunction with each other aspects With.

In a first aspect, the disclosure provides a kind of method for upgrading crude oil.The method includes by crude stream and hydrogen stream Mixing is to obtain crude oil and hydrogen mixture.In addition, the method includes being transmitted to crude oil with hydrogen mixture to arrive 300 The hydrotreating reactor operated at 450 DEG C of temperature and 30 to 200 bars of pressure.Hydrotreating reactor includes hydrotreating Catalyst, the hydrotreating catalyst make crude oil and hydrogen mixture desulfurization and demetalization to generate the mixing of hydrotreating Object.In addition, the method includes that the mixture of the hydrotreating is transmitted to separator unit with by the hydrotreating Mixture is separated into compared with low-boiling fraction and higher fraction.Higher fraction has bigger compared with compared with low-boiling fraction Density of aromatic hydrocarbon and higher boiling point.Higher fraction has at least 500 DEG C of boiling point.The method further includes being Thermal cracking obtains including alkene and aromatic hydrocarbons compared with low-boiling fraction in the steam cracker furnace operated at a temperature of 700 to 900 DEG C Cracking effluent.Finally, the method includes recycling higher fraction so as in hydrotreating reactor upstream and crude oil The further upgrading to promote crude oil is mixed with hydrogen mixture.

In second aspect, the disclosure provides the method according to first aspect, wherein the separative unit includes flash distillation Container and distillation container in the flash chamber downstream.

In the third aspect, the disclosure provides the method according to first or second aspect, wherein passing through the separator Unit separation include: flash chamber, by the mixture of the hydrotreating be separated into first compared with low-boiling fraction and first compared with High boiling fraction.Described first has the boiling spread lower than 350 DEG C compared with low-boiling fraction, and first higher evaporates Divide with the boiling spread higher than 350 DEG C.It is separated by separator unit further include: distillation container is higher by described first Boiling point fraction is separated into second compared with low-boiling fraction and the higher fraction.Described second compared with low-boiling fraction have be higher than 350 DEG C of boiling spreads arrived lower than 500 DEG C, and the higher fraction has the boiling point higher than 500 DEG C.

In fourth aspect, the disclosure provides the method according to the third aspect, wherein the method further includes groups It is described compared with low-boiling fraction to obtain compared with low-boiling fraction compared with low-boiling fraction and described second to close described first.

At the 5th aspect, the disclosure provides the method according to any one of first to fourth aspect, wherein the side Method further comprises the temperature that the crude oil is pre-heated to at least 300 DEG C before mixing with the hydrogen stream.

At the 6th aspect, the disclosure provides the method according to any one of first to the 5th aspect, wherein described add It includes at least one the 8th race's metal, at least one the 6th race's metal or combinations thereof that hydrogen, which handles catalyst,.

At the 7th aspect, the disclosure provides the method according to the 6th aspect, wherein the hydrotreating catalyst packet Include Co and Ni.

In eighth aspect, the disclosure provides the method according to any one of first to the 7th aspect, wherein described add It includes the Mo and W being carried on carrier material that hydrogen, which handles catalyst,.

At the 9th aspect, the disclosure provides the method according to any one of first to eighth aspect, wherein the load Body material includes aluminium oxide.

At the tenth aspect, the disclosure provides the method according to any one of first to the 9th aspect, wherein the original Oil stream has 25 ° to 50 ° of API severe (°).

On the one hand the tenth, the disclosure provides the method according to any one of first to the tenth aspect, wherein wherein The hydrogen stream includes the hydrogen of hydrogen and recycling.

At the 12nd aspect, the disclosure provides the method according to any one of first to the tenth one side, wherein institute Stating hydrotreating reactor includes multiple catalyst layers.

At the 13rd aspect, the disclosure provides the method according to any one of first to the 12nd aspect, wherein institute The liquid hourly space velocity (LHSV) (LHSV) for stating hydrotreating reactor is 0.1 to 2.0h^-1。

In fourteenth aspect, the disclosure provides the method according to any one of first to the 13rd aspect, wherein institute Stating steam cracker furnace includes convection current section and the pyrolysis section in convection current section downstream.

At the 15th aspect, the disclosure provides the method according to fourteenth aspect, wherein the convective region section has The steam and light fraction ratio of 0.3:1 to 2:0.1.

At the 16th aspect, the disclosure provides the method according to the 14th or the 15th aspect, wherein the convection current Section realizes 0.05 to 2 seconds reaction residence times.

At the 17th aspect, the disclosure provides the method according to any one of first to the 16th aspect, wherein institute The aromatic hydrocarbons for stating cracking effluent includes one of benzene, toluene and dimethylbenzene or a variety of.

At the 18th aspect, the disclosure provides the method according to any one of first to the 17th aspect, wherein institute The method of stating further comprises the temperature that the cracking effluent is cool below to 200 DEG C.

At the 19th aspect, the disclosure provides the method according to any one of first to the 18th aspect, wherein institute The method of stating further comprises that the cracking effluent is delivered to gas-liquid separator, oil-liquid/gas separator or combinations thereof.

At the 20th aspect, the disclosure provides the method according to any one of first to the 19th aspect, wherein institute The method of stating further comprises separating alkene by the cracking effluent in fractionator.

It should be apparent that it can be in the spirit and scope for not departing from required theme for those skilled in the art In the case where described embodiment is carry out various modifications.Therefore, it is intended that this specification covers to various described implementations The modifications and variations of example, condition are that such modifications and variations are in the range of the appended claims and its equivalent.

Through the disclosure, range is provided.It is contemplated that each discrete value included by range is also included.In addition, It is also envisioned that can each discrete value is formed as included by clear scope of disclosure range.

Claims

1. a kind of method for upgrading crude oil comprising:

Crude stream is mixed with hydrogen stream to obtain crude oil and hydrogen mixture；

The crude oil and hydrogen mixture are transmitted to it is being operated at 300 to 450 DEG C of temperature and 30 to 200 bars of pressure plus Hydrogen treatment reactor, the hydrotreating reactor include hydrotreating catalyst, and the hydrotreating catalyst makes the original Oil generates the mixture of hydrotreating with hydrogen mixture desulfurization and demetalization；

It is lower the mixture of the hydrotreating to be separated into that the mixture of the hydrotreating is transmitted to separator unit Boiling point fraction and higher fraction, wherein bigger virtue compared with the higher fraction has with described compared with low-boiling fraction Hydrocarbon concentration and higher boiling point, and wherein the higher fraction has at least 500 DEG C of boiling point；

In the steam cracker furnace operated at a temperature of being 700 to 900 DEG C described in thermal cracking compared with low-boiling fraction to be included The cracking effluent of alkene and aromatic hydrocarbons；With

The higher fraction is recycled so as in the hydrotreating reactor upstream and the crude oil and hydrogen mixture Mix the further upgrading to promote the crude oil.

2. according to the method described in claim 1, wherein the separative unit includes flash chamber and under the flash chamber The distillation container of trip.

3. method according to claim 1 or 2, wherein including: by separator unit separation

The mixture of the hydrotreating is separated into first and evaporated compared with low-boiling fraction and the first higher by flash chamber Point, wherein described first has the boiling spread lower than 350 DEG C compared with low-boiling fraction, and the first higher fraction has There is the boiling spread higher than 350 DEG C；With

Container is distilled, the first higher fraction seperation is evaporated for second compared with low-boiling fraction and the higher Point, wherein described second has the boiling spreads arrived higher than 350 DEG C lower than 500 DEG C compared with low-boiling fraction, and described more high boiling Point fraction has the boiling point higher than 500 DEG C.

4. according to the method described in claim 3, it further comprises combination described first compared with low-boiling fraction and described second It is described compared with low-boiling fraction to obtain compared with low-boiling fraction.

5. method according to any of the preceding claims, further comprise by the crude oil with the hydrogen stream At least 300 DEG C of temperature is pre-heated to before mixing.

6. method according to any of the preceding claims, wherein the hydrotreating catalyst include at least one 8 race's metals, at least one the 6th race's metal or combinations thereof.

7. according to the method described in claim 7, wherein the hydrotreating catalyst includes Co and Ni.

8. method according to any of the preceding claims, wherein the hydrotreating catalyst includes being carried on carrier Mo and W on material.

9. method according to any of the preceding claims, wherein the carrier material includes aluminium oxide.

10. method according to any of the preceding claims, wherein the crude stream has 25 ° to 50 ° of API severe (°)。

11. method according to any of the preceding claims, wherein the hydrogen stream includes the hydrogen of hydrogen and recycling Gas.

12. method according to any of the preceding claims, wherein the hydrotreating reactor includes multiple catalysis Oxidant layer.

13. method according to any of the preceding claims, wherein the liquid hourly space velocity (LHSV) of the hydrotreating reactor It (LHSV) is 0.1 to 2.0h^-1。

14. method according to any of the preceding claims, wherein the steam cracker furnace include convection current section and The pyrolysis section in convection current section downstream.

15. according to the method for claim 14, wherein the convective region section has the steam of 0.3:1 to 2:0.1 and gently evaporates Divide ratio.

16. method according to claim 14 or 15, wherein when the convective region section realizes reaction delay in 0.05 to 2 seconds Between.

17. method according to any of the preceding claims, wherein the cracked stream go out object the aromatic hydrocarbons include benzene, One of toluene and dimethylbenzene are a variety of.

18. method according to any of the preceding claims further comprises being cooled to the cracking effluent Temperature lower than 200 DEG C.

19. method according to any of the preceding claims further comprises being delivered to the cracking effluent Gas-liquid separator, oil-liquid/gas separator or combinations thereof.

20. method according to any of the preceding claims further comprises in fractionator by the cracked stream Object separates alkene out.